Organic high-spin systems: Synthesis,electrochemical and spectroscopic studies of π-extended tetraaryl m-phenylenediamines

Three highly π-extended tetraaryl-1,3-phenylenediamines for charged high-spin molecular systems were successfully synthesized using Suzuki coupling. Their electrochemical and spectroscopic properties were also examined. They showed blue fluorescence. The dications derived from highly π-extended tetraaryl-1,3-phenylenediamines were generated and characterized by electron transfer stopped-flow method.     

Correlative Sparsity in Primal-Dual Interior-Point Methods for LP,SDP, and SOCP

Exploiting sparsity has been a key issue in solving large-scale optimization problems. The most time-consuming part of primal-dual interior-point methods for linear programs, second-order cone programs, and semidefinite programs is solving the Schur complement equation at each iteration, usually by the Cholesky factorization. The computational efficiency is greatly affected by the sparsity of the coefficient matrix of the equation which is determined by the sparsity of an optimization problem (linear program, semidefinite program or second-order cone program). We show if an optimization problem is correlatively sparse, then the coefficient matrix of the Schur complement equation inherits the sparsity, and a sparse Cholesky factorization applied to the matrix results in no fill-in. S. Kim’s research was supported by Kosef R01-2005-000-10271-0 and KRF-2006-312-C00062.     

Bonding structure of phenylacetylene on hydrogen-terminated Si(111) and Si(100): surface photoelectron spectroscopy analysis and ab initio calculations

Interfaces between phenylacetylene (PA) monolayers and two silicon surfaces, Si(111) and Si(100), are probed by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and the results are analyzed using ab initio molecular orbital calculations. The monolayer systems are prepared via the surface hydrosilylation reaction between PA and hydrogen-terminated silicon surfaces. The following spectral features are obtained for both of the PA-Si(111) and PA-Si(100) systems: a broad π-π* shakeup peak at 292 eV (XPS), a broad first ionization peak at 3.8 eV (UPS), and a low-energy C 1s → π* resonance peak at 284.3 eV (NEXAFS). These findings are ascribed to a styrene-like π-conjugated molecular structure at the PA-Si interface by comparing the experimental data with theoretical analysis results. A conclusion is drawn that the vinyl group can keep its π-conjugation character on the hydrogen-terminated Si(100) [H:Si(100)] surface composed of the dihydride (SiH(2)) groups as well as on hydrogen-terminated Si(111) having the monohydride (SiH) group. The formation mechanism of the PA-Si(100) interface is investigated within cluster ab initio calculations, and the possible structure of the H:Si(100) surface is discussed based on available data.     

Catalysis of redox reactions by Ag@TiO<Subscript>2</Subscript> and Fe<Superscript>3+</Superscript>-doped Ag@TiO<Subscript>2</Subscript> core–shell type nanoparticles

Ag nanoparticles encapsulated by TiO₂ shells have the ability to catalyze redox reactions on their surface. By continually monitoring by use of UV–visible spectroscopy it was found that the surface charge of both TiO₂-coated and uncoated colloidal silver particles changed after chemical electron injection. The charging and discharging process of Ag@TiO₂ vary, depending on the different Ag content of the core–shell nanoparticles. In order to enhance the stability of Ag@TiO₂ colloids, Fe³⁺ was doped into the lattice of the TiO₂ shells. The experimental results showed that the Fe³⁺ ions have the capacity to store and transfer electrons. Furthermore, the charging and discharging rate can be controlled by changing the thickness of the TiO₂ shells, because they are limited by the diffusion distance of electrons through the TiO₂ shells.     

Test compounds for detecting the silanol effect on the elution of ionized amines in reversed‐phase LC

The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC.     

Two-dimensional and three-dimensional Fermi surfaces of superconducting BaFe2(As(1-x)P(x))2 and their nesting properties revealed by angle-resolved photoemission spectroscopy

We have studied the three-dimensional shapes of the Fermi surfaces (FSs) of BaFe(2)(As(1-x)P(x))(2) (x=0.38), where superconductivity is induced by isovalent P substitution and by angle-resolved photoemission spectroscopy. Moderately strong electron mass enhancement has been identified for both the electron and hole FSs. Among two observed hole FSs, the nearly two-dimensional one shows good nesting with the outer two-dimensional electron FS, but its orbital character is different from the outer electron FS. The three-dimensional hole FS shows poor nesting with the electron FSs. The present results suggest that the three dimensionality and the difference in the orbital character weaken FS nesting while partial nesting among the outer electron FSs of d(xy) character and/or that within the three-dimensional hole FS becomes dominant, which may lead to the nodal superconductivity.     

Formation mechanism of element distribution in glass under femtosecond laser irradiation

We report on the formation mechanism of element distribution in glass under high-repetition-rate femtosecond laser irradiation. We simultaneously focused two beams of femtosecond laser pulses inside a glass and confirmed the formation of characteristically shaped element distributions. The results of the numerical simulation in which we considered concentration- and temperature-gradient-driven diffusions were in excellent qualitative agreement with the experimental results, indicating that the main driving force is the sharp temperature gradient. Since the composition of a glass affects its refractive index, absorption, and luminescence property, the results in this study provide a framework to fabricate a functional optical device such as optical circuits with a high-repetition-rate femtosecond laser.